High temperature sealing material

This is a continuation of U.S. Ser. No. 09/459,535, filed Dec. 13, 1999, now abandoned, and claims the benefit of U.S. Provisional Application No. 60/112,039, filed Dec. 15, 1998.

BACKGROUND OF THE INVENTION

The invention concerns a glass composition for use as sealing material in fuel cells! preferably in the solid oxide fuel cells (SOFC) of the stacked planar type. Typically, such fuel cells are composed of Y-stabilized ZrO₂, (YSZ) electrolyte with electrodes and contact layers to the electron conducting plate Interconnect (IC), which makes the series connection between the cells. Gas tight sealings are vitally important for the performance, durability and safety operation of the fuel cells including the manifold and heat exchanger.

The difficulties in providing a suitable sealing material are numerous:

The sealing material should be able to adhere to the fuel cell components at a heat treatment not higher than 1300° C. which is the maximum temperature heat treatment of a fuel cell stack, and be resilient in order to take up deformations, e.g. due to TEC differences between the fuel cell components, and at the same being able to withstand a certain overpressure at the operation temperature which require a viscosity of more than 10⁵dPas·s. The thermal expansion coefficient (TEC) should be in the range 9-13·10⁻⁶K⁻¹in order not to initiate cracks in the fuel cell components. Furthermore, the sealing material has to be stable over a time span of say 40.000 h without deteriorating crystallization or reactions with the other materials as well as with the ambient gasses, atmosphere containing steam, methane, hydrogen, carbonmonoxide and carbondioxide or nitrogen and oxygen.

Glass or glass ceramic seals may fulfil the requirements established above and according to literature quite a range of potential glasses have been reported:

<tables><table frame="none" colsep="0" rowsep="0"><tgroup align="left" colsep="0" rowsep="0" cols="1"><colspec colname="1" colwidth="217pt" align="center" /><thead><row><entry namest="1" nameend="1" rowsep="1">TABLE 1</entry></row><row><entry namest="1" nameend="1" align="center" rowsep="1" /></row><row><entry>SOFC SEALING MATERIALS</entry></row><row><entry namest="1" nameend="1" align="center" rowsep="1" /></row></thead><tbody valign="top"><row><entry /></row></tbody></tgroup><tgroup align="left" colsep="0" rowsep="0" cols="2"><colspec colname="offset" colwidth="28pt" align="left" /><colspec colname="1" colwidth="189pt" align="left" /><tbody valign="top"><row><entry /><entry>Alkaline oxide silicate glasses</entry></row><row><entry /><entry>Na₂O—CaO—SiO₂</entry></row><row><entry /><entry>Li₂O—ZnO—Al₂O₃—SiO₂and MgO—ZnO—SiO₂</entry></row><row><entry /><entry>Alkali-Al₂O₃—SiO₂</entry></row><row><entry /><entry>Alkali-B₂O₃—SiO₂</entry></row><row><entry /><entry>Na₂O—SiO₂</entry></row><row><entry /><entry>Li₂O—SiO₂</entry></row><row><entry /><entry>Mica Glass Ceramics</entry></row><row><entry /><entry>Commercially available mica glass-ceramic</entry></row><row><entry /><entry>Alkaline-Earth Oxide Borosilicate/Silicaborate Glasses</entry></row><row><entry /><entry>Alkaline-Earth-B₂O₃—SiO₂</entry></row><row><entry /><entry>SrO—La₂O₃—Al₂O₃—B₂O₃—SiO₂/</entry></row><row><entry /><entry>SiO₂—B₂O₃</entry></row><row><entry /><entry>BaO—As₂O₃—Al₂O₃—B₂O₃—SiO₂</entry></row><row><entry /><entry>Alkaline-Earth Alumina Silicates</entry></row><row><entry /><entry>SiO₂based glass-ceramics</entry></row><row><entry /><entry>MgO—Al₂O₃—SiO₂</entry></row><row><entry /><entry>CaO—Al₂O₃—SiO₂</entry></row><row><entry /><entry namest="offset" nameend="1" align="center" rowsep="1" /></row></tbody></tgroup></table></tables>

According to Ley et al. (1996), each of these glass types have a drawback: the alkalis and alkali silicates and borates will react with the fuel cell components. The alkali borate glasses have too low TEC and soda-lime glasses too low viscosity.

In contrast several glass compositions within the SrO—La₂O₃—Al₂O₃—B₂O₃—SiO₂system should be suitable (K. L. Ley, M. Krumpelt, R. Kumar, J. H. Meiser &amp; I. Bloom, 1996, J. Mater. Res., Vol. 11, No 6, pages 1489-1493).

The present invention is in contrast to the conclusion of the authors above based on highly viscous polymerized alkali-alumina-silicate glass seals, which are reluctant to crystallize at elevated temperature. An example of a highly polymerized glass is pure SiO₂glass, which has a polymerized 3D network (as the crystalline phase, quartz) based on SiO₄⁴⁻ tetrahedra, where each oxygen ion connects two Si ions (B. E. Warren &amp; Biscoe, 1938, J. Am. Ceram. Soc. 21, page 29). By addition of group I, II and III metal oxides this network is broken and the softening point, the viscosity and the melting point decreases significantly. It is possible to retain a polymerized structure of the melt with a high viscosity by substituting SiO₂with NaAlO₂(D. C. Boyd &amp; D. A. Thompson, in Ullmann, Vol. 11, page 815). Accordingly, a NaAlSi₃O₈melt has a high viscosity of 10^8.5dPas·s at 1120° C. (H. Rawson, 1967, Academic Press, London and New York, page 89). This melt is assumed to have a 3D network (Si_1-x, Al_x)O₄^4−x− network structure, where xNa⁺ compensate the extra negative charge, similar to the 3D network in the mineral albite with the same composition. Crystallization from such a highly viscous melt held nearly 100° C. below the melting point may take years due to the high viscosity (H. Rawson, 1967). By addition or subtraction of NaAlSiO₄, SiO₂, it is possible to reach two eutectic melting temperatures at 1062° and 1068° at compositions: NaAlSiO₄: SiO₂, 37.0:63.0 wt % and 65.0:35 wt %, respectively (J. F. Schairer, J. Geol. 58, No 5, 514, 1950). For the system: KAlSiO₂, SiO₂, an eutectic point of 990±20° C. may be obtained at a composition of KAlSiO₄: SiO₂equal to 32.8:67.2 wt % (J. F. Schairer, N. L. Bowen, Bull Soc, Geol. Finland, 20.74 (1947).

The TEC of a NaAlSi₃O₈glass is 7.5·10⁻⁶K⁻¹, which is lower than the SOFC components 10.0-13·10⁻⁶. The TEC of the albite glass can be increased slightly by addition of NaAlO₂, whereas a value of 10.4·10⁻⁶K⁻¹may be obtained by addition of Na₂O giving a cation composition of Na_3.33Al_1.67Si₅(O. V. Mazurin, M. V. Streltsina &amp; T. P. Shvaikoshvaikoskaya, Handbook of glass data, part C, page 371, from K. Hunold &amp; R. Brûckner, 1980a, Glastech. Ber. 53, 6, pages 149-161). Higher values up to more than 12×10⁻⁶K⁻¹can be obtained by further addition of Na₂O according to these authors.

An example of a NaAlSi₃O₈+Na₂O TEC matched glass for sealing yttria stabilized zirconia is shown in FIG. <b>1</b>. Addition of K₂O will have an even higher effect on the TEC.

Addition of Na₂O and K₂O alone will decrease the viscosity and the T_glassand T_softeningas illustrated in Table 2 for Na₂O, which will be necessary for operation temperatures below 1000° C.

<tables><table frame="none" colsep="0" rowsep="0"><tgroup align="left" colsep="0" rowsep="0" cols="3"><colspec colname="offset" colwidth="140pt" align="left" /><colspec colname="1" colwidth="35pt" align="center" /><colspec colname="2" colwidth="42pt" align="center" /><thead><row><entry /><entry namest="offset" nameend="2" rowsep="1">TABLE 2</entry></row><row><entry /><entry namest="offset" nameend="2" align="center" rowsep="1" /></row><row><entry /><entry>T_g(° C.)</entry><entry>T_s(° C.)</entry></row><row><entry /><entry namest="offset" nameend="2" align="center" rowsep="1" /></row></thead><tbody valign="top"><row><entry /></row></tbody></tgroup><tgroup align="left" colsep="0" rowsep="0" cols="3"><colspec colname="1" colwidth="140pt" align="left" /><colspec colname="2" colwidth="35pt" align="center" /><colspec colname="3" colwidth="42pt" align="center" /><tbody valign="top"><row><entry>11.8 Na₂O − 19.4Al₂O₃− 68.7SiO₂</entry><entry>786</entry><entry>910</entry></row><row><entry>17.1 Na₂O − 14.9Al₂O₃− 68.0SiO₂</entry><entry>515</entry><entry>607</entry></row><row><entry>11.8 Na₂O − 19.4Al₂O₃− 68.7SiO₂+ YSZ</entry><entry>814</entry><entry>929</entry></row><row><entry namest="1" nameend="3" align="center" rowsep="1" /></row></tbody></tgroup></table></tables>

Alkali-addition, however, will cause an increased reaction rate with the other fuel cell components and an evaporation of sodium and potassium, so that this solution is best suited for low operation temperatures. Small amounts of BO₃addition can also be used to decrease the melt temperature and viscosity. An alternative to the addition of alkalies in order to increase the TEC is to use fillers with a high TEC and (Y. Harufuji 1992: Japanese Patent No 480,077 A2) and (Y. Harufuji 1994, Japanese Patent No 623,784 A2) thus Harufuji mentions different fibres of carbon, boron, SiC, polytitanocarbosilane, ZrO₂and Al₂O₃and powders of Al₂O₃, ZrO₂, SiO₂, MgO, Y₂O₃and CaO and Al, Ag, Au and Pt. To this list we can add stabilized ZrO₂, TiO₂, MgO—MgAl₂O₄composites, (Mg,Ca)SiO₃, Mg₂SiO₄, MgSiO₃, CaSiO₃, CaZrO₃and M^IIAlSi₂O₈, where M^II=Ca, Sr and/or Ba (rare earth oxides, e.g. CeO₂, Eu₂O₃and ThO₂) (Li₂Si₂O₅may be used at temperatures below 1000° C.).

Other alkalisilicates may be used as fillers for low temperature operation. A combination of alkali and filler addition can be used to obtain optimal TEC, viscosity and the softening point T_s. Also addition of small amounts (&lt;wt %) B₂O₃instead of or together with Na₂O combined with addition of high TEC fillers mentioned above is a possibility. The filler addition will reduce the exposed surface of the glass and thus the evaporation of the more volatile constituents of the glass.

Deteriorating Reactions May Involve:

(1) SiO evaporation may occur under reducing condition on the anode side condensation may take place in other areas of the fuel cell system. Apparently this process is slow.

(2) Volatile sodium and potassium may react with the other fuel cell materials, e.g. the chromite of the interconnection plate. The evaporation is strongly influenced by the sodium surplus of the glass. For this reason the sealing glasses with alkali/Al-ratios above 1 should only be used in fuel cells with low operation temperatures.

SUMMARY OF THE INVENTION

According to the invention there is provided a glass composition comprising a glass matrix with main components consisting of SiO₂, Al₂O₃and one or more compounds from group I metal oxides, and a filler material evenly dispersed in the matrix, wherein the filler material consists of particles of one or more refractive compounds from the group: (Al₂O₃, MgO,) rare earth oxides, MgO—MgAl₂O₄composites, stabilized zirconia, (MgCa)SiO₃, Mg₂SiO₄, MgSiO₃CaSiO₃, CaZrO₃, ThO₂, TiO₂and the M^IIAlSi₂O₈, where M^II=Ca, Sr and/or Ba. For low temperature application alkalisilicate fillers may be used.

The filler material is added to the sealing glass in order to adjust the thermal expansion coefficient, so that it matches the TEC of the other parts of the fuel cell in addition the stability of the glass may be improved and the viscosity increased.

Preferred embodiments of the composition contain Na₂O or K₂O or both in amounts such that the stoichiometric molar ratio of Al₂O₂to Na₂O or K₂O is in the range of 0.1-1.3 in order to reach an optimum TEC, while at the same time avoiding too much alkali metal that may react with the other materials in the cell stack.

One or more compounds of group II metal oxide may be components of the glass matrix. Known glass compositions with main components comprising SiO₂, Al₂O₃, and one or more compounds from group I or group II metal oxides are advantageous for sealing fuel cells with gas separators of La—Sr/Ca/Mg—Cr/V—O interconnections of ceramic material or a metal alloy, e.g., Cr—Fe—Y₂O₃material and with an operating temperature above 600° C. In particular, compositions that within the glass have evenly dispersed a refractive filler material consisting of particles of one or more compounds from the group: MgO, MgO—MgAl₂O₄composites, stabilized zirconia, rare earth oxides (especially Eu₂O₃and CeO₂), ThO₂, TiO₂, (MgCa)SiO₃, Mg₂SiO₃, CaSiO₃, CaZrO₃, and M^IIAlSi₂O₈, (M^II=Ca, Sr or Ba).

In a preferred embodiment of the invention commercially available feldspar or nepheline syenite starting materials may be used for making the basic glass material.

The starting material is melted at about 1550° C. for one hour in an alumina or platinum crucible. The melted material is then quenched in water, crushed and ground to glass powder with a particle size of less than 90 μm. The glass powder having a TEC of about 75×10⁻⁷/K is then mixed with a filler, e.g. MgO (TEC 130×10⁻⁷/K) with a grain size of less than 10-40 μm in ratio of 2:3.5 (vol.) in order to obtain a TEC of 110×10⁻⁷/K.

Glass sealing are produced by filling the mixed powder into graphite forms followed by stamping and removal of excess of powder. The powder is then sintered in a furnace in N₂-atmosphere at 750° C. for 5 hours and at 1300° C., for one hour. Glass seals for narrow gaps &lt;1 mm (e.g. in the electrode area) are produced by tape-casting of glass and filler mixtures.

EXAMPLE 1

A commercial available feldspar (SiO₂=68.4, Al₂O₃=19.1, Fe₂O₃=0.1, CaO=2.0, Na₂O=7.5=K₂O=2.8; melt point 1270° C.) is melted at 1550° C. in one hour in a Al₂O₃or Pt crucible. Subsequently, the melt is quenched in water from 1000° C., crushed and grounded to ≦90 μm in a porcelain mill half filled with porcelain balls. The glass powder thus obtained with a TEC of ˜75×10⁻⁷/K is mixed with the preferred filler of calcined (1700° C.) MgO with a TEC of 130×10⁻⁷/K and a grain size of 10-40 μm in a ratio of glass MgO of 2:3.5 in order to obtain a TEC of 110×10⁻⁷/K. Glass sealings in the shape of triangular rods are produced by filling the mixed powder into a graphite cast form with V-shaped grooves, followed by stamping and removal of excess powder. The composition is sintered in a furnace in N₂-atmosphere at 750° C. for 5 hours and at 1300° C. for 2 hours. The produced triangular rods may be machined to the wanted dimensions. If the viscosity is too high addition of small amounts (&lt;5%) B₂O₃and/or Na₂O may be an advantage.

EXAMPLE 2

As in Example 1 except that the commercial feldspar powder (&lt;90 μm) is mixed with the calcined (1700° C.) MgO powder and melted in graphite cast forms above 1300° C. for 5 hours.

EXAMPLE 3

Glass is produced from dried powder of:

<tables><table frame="none" colsep="0" rowsep="0"><tgroup align="left" colsep="0" rowsep="0" cols="4"><colspec colname="offset" colwidth="42pt" align="left" /><colspec colname="1" colwidth="28pt" align="left" /><colspec colname="2" colwidth="70pt" align="right" /><colspec colname="3" colwidth="77pt" align="left" /><thead><row><entry /><entry namest="offset" nameend="3" align="center" rowsep="1" /></row></thead><tbody valign="top"><row><entry /><entry>SiO₂</entry><entry>1442.08</entry><entry>g (&lt;1 μm)</entry></row><row><entry /><entry>Al₂O₃</entry><entry>407.84</entry><entry>g (&lt;1 μm)</entry></row><row><entry /><entry>Na₂CO₃</entry><entry>423.9</entry><entry>g (&gt;1 μm)</entry></row><row><entry /><entry namest="offset" nameend="3" align="center" rowsep="1" /></row></tbody></tgroup></table></tables>

The powder is mixed in a 5 liter PE bottle with 20-30 mm porcelain balls for 24 hours. The powder is poured into Al₂O₃crucibles and heated to 1550° C. for 2 hours and subsequently quenched from 600° C. in H₂O. The quenched materials thus obtained is crushed to &lt;9 mm grains and grounded in a porcelain mill for 17 hours with 20-30 mm sized balls to glass powder with a particle size of less than 100 μm.

The glass powder is then mixed with 50 wt %, ZrO₂stabilized with 8 mole % Y₂O₃spherical 40-60 μm powder, calcined at 1700° C. and poured into a graphite cast form, as described in Example 1, and then sintered at 750° C. for 5 hours and at 1125° C. for one hour followed by oven cooling. At FIG. 1 the expansion curve is given for this mixture.

EXAMPLE 4

Glass, produced as in Example 1 or 2, and a filler material (e.g. MgO or yttria stabilized zirconia) are mixed by ball milling for 2 hours with a dispersing agent, polyvinylpyrrolidon dissolved in methylethylketon and ethanol. Subsequently, a binder mixture of polyvinylbutyral, dibutylphtalat, polyethylenglycol, Additol (Hoechst) (dissolved in methylethylketon and ethanol) is added and the ball milling is continued for 24 hours. The so-produced slurry is casted onto a moving substrate and allowed to dry for 24 hours before removal.

The green tapes are cut into the desired dimensions and are applied to the sealing area in the green state. The sealing is achieved by a subsequent heat treatment up to 1200° C. using a temperature ramp below 50° C./h in the range up to 500° C.

EXAMPLE 5

A composition according to Beall (1986) (J. H. Simmons, D. R. Uhlmann, G. H. Beall (eds.) in 1982: Advances in Ceramics, Vol. 4, page 291, Am. Ceram. Soc.) of:

<tables><table frame="none" colsep="0" rowsep="0"><tgroup align="left" colsep="0" rowsep="0" cols="3"><colspec colname="offset" colwidth="56pt" align="left" /><colspec colname="1" colwidth="28pt" align="left" /><colspec colname="2" colwidth="133pt" align="center" /><thead><row><entry /><entry namest="offset" nameend="2" align="center" rowsep="1" /></row></thead><tbody valign="top"><row><entry /><entry>SiO₂</entry><entry>38.9</entry></row><row><entry /><entry>Al₂O₃</entry><entry>13.7</entry></row><row><entry /><entry>MgO</entry><entry>11.0</entry></row><row><entry /><entry>SrO</entry><entry>10.1</entry></row><row><entry /><entry>BaO</entry><entry>14.0</entry></row><row><entry /><entry>MgF₂</entry><entry>12.6</entry></row><row><entry /><entry namest="offset" nameend="2" align="center" rowsep="1" /></row></tbody></tgroup></table></tables>

is produced by mixing the oxide components and MgF₂in a high intensity vibration mill with Al₂O₃balls. The composition is then melted at 1550° C. for one hour. The thus produced glass is milky with a TEC of 110×10⁻⁴/K according to Beall (1986). The glass is rather viscous and did not adhere well to the cell stack material. The adherence to these materials can be improved by addition of small amounts (up to 5%) of B₂O₃and/or alkaline metals.